EP2871157B1 - Verfahren zur herstellung eines lithiumeisenphosphat-nanopulvers - Google Patents
Verfahren zur herstellung eines lithiumeisenphosphat-nanopulvers Download PDFInfo
- Publication number
- EP2871157B1 EP2871157B1 EP14737596.8A EP14737596A EP2871157B1 EP 2871157 B1 EP2871157 B1 EP 2871157B1 EP 14737596 A EP14737596 A EP 14737596A EP 2871157 B1 EP2871157 B1 EP 2871157B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- iron phosphate
- preparing
- lithium iron
- nanopowder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims description 66
- 239000011858 nanopowder Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 53
- 239000002245 particle Substances 0.000 claims description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- 239000011247 coating layer Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 239000012692 Fe precursor Substances 0.000 claims description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 15
- 239000012688 phosphorus precursor Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000904 FeC2O4 Inorganic materials 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- NPLZZSLZTJVZSX-UHFFFAOYSA-L iron(2+);oxalate;dihydrate Chemical compound O.O.[Fe+2].[O-]C(=O)C([O-])=O NPLZZSLZTJVZSX-UHFFFAOYSA-L 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims description 2
- AJVRSHNXSHMMCH-UHFFFAOYSA-K iron(III) citrate monohydrate Chemical compound O.[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O AJVRSHNXSHMMCH-UHFFFAOYSA-K 0.000 claims description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- DDXPLCBTGWFAIG-UHFFFAOYSA-N triazanium;phosphate;trihydrate Chemical compound [NH4+].[NH4+].[NH4+].O.O.O.[O-]P([O-])([O-])=O DDXPLCBTGWFAIG-UHFFFAOYSA-N 0.000 claims description 2
- LRPQHRZRXAFVLP-UHFFFAOYSA-K trilithium phosphate dodecahydrate Chemical compound [Li+].[Li+].[Li+].O.O.O.O.O.O.O.O.O.O.O.O.[O-]P([O-])([O-])=O LRPQHRZRXAFVLP-UHFFFAOYSA-K 0.000 claims description 2
- 229910000149 boron phosphate Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000001027 hydrothermal synthesis Methods 0.000 description 20
- 239000007810 chemical reaction solvent Substances 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- -1 lithium iron phosphate compound Chemical class 0.000 description 14
- 239000006182 cathode active material Substances 0.000 description 13
- 229960004418 trolamine Drugs 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000001308 synthesis method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 150000002642 lithium compounds Chemical class 0.000 description 5
- 239000010450 olivine Substances 0.000 description 5
- 229910052609 olivine Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
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- 150000002461 imidazolidines Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/30—Three-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a method for preparing a lithium iron phosphate nanopowder.
- lithium secondary batteries having high energy density and voltage, a long life cycle, and a low self-discharge rate are being commercialized and widely used.
- lithium cobalt oxide LiCoO 2
- the cobalt oxide containing lithium is unstable and expensive, the mass production of lithium secondary batteries including thereof is difficult.
- lithium iron phosphate (LiFePO 4 ) compound having a voltage against lithium of ⁇ 3.5 V, a high volume density of 3.6 g/cm 3 , and a theoretical capacity of 170 mAh/g, as well as good stability at high temperature, and being cheap when compared to the lithium cobalt oxide, is being viewed as a suitable cathode active material for a lithium secondary battery.
- a solid-state reaction method or a liquid-state reaction method such as a hydrothermal synthesis method and a supercritical hydrothermal synthesis is known.
- a glycothermal synthesis method is using a non-aqueous solvent such as ethylene glycol or diethylene glycol as a reaction solvent has been developed.
- the hydrothermal synthesis method and the supercritical hydrothermal synthesis method the preparation of the lithium iron phosphate nanopowder is performed under high temperature and high pressure conditions, giving rise to safety concerns.
- the control of the particle size and the particle size distribution of the lithium iron phosphate nanopowder may be difficult.
- JP 2012123909 A discloses a method for preparing olivine-type lithium iron phosphate having a size of 200 nm or less comprising: mixing a lithium precursor, an iron precursor and phosphoric acid in triethanol amine, heating the mixture at 190-210°C, and washing and drying the obtained product.
- EP 2 413 402 A1 and WO 2011/132961 A2 disclose olivine-type lithium iron phosphate nanopowders to be used as a cathode active material in a lithium secondary battery.
- An aspect of the present invention provides a method for preparing a lithium iron phosphate nanopowder using a novel reaction solvent to resolve the above-described limitations, by which a reaction may be performed under relatively low pressure conditions when compared to a common hydrothermal synthesis method, a supercritical hydrothermal synthesis method, or a glycothermal synthesis method.
- a high temperature/high pressure reactor may not be used, so that process safety and economic feasibility may be secured, while uniform particle size may be obtained and a particle size distribution may be controlled.
- a method for preparing a lithium iron phosphate nanopowder comprising the steps of: (a) preparing a non-aqueous mixture solution by adding a lithium precursor, an iron precursor and a phosphorus precursor in a non-aqueous triethanolamine solvent; and (b) putting the non-aqueous mixture solution into a reactor and heating to prepare the lithium iron phosphate nanopowder under pressure conditions of 1 to 10 bar, wherein Step (b) is performed at a temperature range of 150 to 335°C
- a reaction may be performed under relatively lower pressure conditions when compared to a common hydrothermal synthesis method, a supercritical hydrothermal synthesis method and a glycothermal synthesis method, such that a high temperature/high pressure reactor may not be used and so, process safety and economic feasibility may be secured, while uniform particle size may be obtained and particle size distribution may be controlled.
- a lithium secondary battery including the lithium iron phosphate nanopowder thus prepared as a cathode active material has good capacity and stability.
- a method for preparing a lithium iron phosphate nanopowder using a novel reaction solvent under relatively low pressure conditions is provided to resolve the safety issue and high cost brought about in a hydrothermal synthesis method, a supercritical hydrothermal synthesis method, or a glycothermal synthesis method, in which a reaction is performed under high temperature/high pressure conditions, so an high temperature/high pressure reactor (for example, autoclave) is used.
- an high temperature/high pressure reactor for example, autoclave
- process safety and the economic feasibility may be largely improved when compared to the common hydrothermal synthesis method, the supercritical hydrothermal synthesis method, or the glycothermal synthesis method, and a lithium iron phosphate nanopowder having uniform particle size may be obtained.
- a method for preparing a lithium iron phosphate nanopowder comprising the steps of: (a) preparing a non-aqueous mixture solution by adding a lithium precursor, an iron precursor and a phosphorus precursor in a non-aqueous triethanolamine solvent; and (b) putting the non-aqueous mixture solution into a reactor and heating to prepare the lithium iron phosphate nanopowder under pressure conditions of 1 to 10 bar, wherein Step (b) is performed at a temperature range of 150 to 335°C
- the method may further include (c) heat treating the lithium iron phosphate nanopowder at a temperature range of 400 to 900°C to form a coating layer on a portion or the whole of the surface of the individual particle of the nanopowder.
- a lithium precursor, an iron precursor, and a phosphorus precursor are prepared and added in a reaction solvent to prepare a homogeneous mixture solution (Step (a)).
- the lithium precursor thus added may be at least one selected from the group consisting of lithium acetate dihydrate (CH 3 COOLi ⁇ 2H 2 O), lithium hydroxide monohydrate (LiOH ⁇ H 2 O), lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), lithium phosphate (Li 3 PO 4 ), lithium phosphate dodecahydrate (Li 3 PO 4 ⁇ 12H 2 O), lithium oxalate (Li 2 C 2 O 4 ), and a mixture thereof.
- the iron precursor added may be at least one selected from the group consisting of iron citrate (FeC 6 H 5 O 7 ), iron citrate hydrate (FeC 6 H 5 O 7 ⁇ nH 2 O), ferrous sulfate heptahydrate (FeSO 4 ⁇ 7H 2 O), iron (II) oxalate dihydrate (FeC 2 O 4 ⁇ 2H 2 O), iron acetyl acetonate (Fe(C 5 H 7 O 2 ) 3 ), iron phosphate dihydrate (FePO 4 ⁇ 2H 2 O) ferric hydroxide (FeO(OH)), and a mixture thereof.
- the phosphorus precursor added may be at least one selected from the group consisting of tri-ammonium phosphate trihydrate ((NH 4 ) 3 PO 4 ⁇ 3H 2 O), ammonium phosphate ((NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), phosphoric acid (H 3 PO 4 ), and a mixture thereof.
- the mixing ratio of the lithium precursor, the iron precursor and the phosphorus precursor during the forming of the mixture solution is not specifically limited, and may be, for example, 0.1-10:1:0.1-10 by the molar ratio.
- the iron precursor may be added from about 0.005 to about 1 parts by weight based on 1 part by weight of the triethanolamine reaction solvent, and the lithium precursor and the phosphorus precursor may be added by corresponding molar ratios considering the amount of the iron precursor.
- a stirring step may be further conducted during preparing the mixture solution so that the lithium precursor, the iron precursor and the phosphorus precursor may be homogeneously dispersed in the triethanolamine reaction solvent.
- reaction solvent is triethanolamine which is a non-aqueous solvent and has a relatively high boiling point.
- the boiling point of the triethanolamine is about 335°C.
- the lithium iron phosphate nanopowder was verified to be synthesized at temperature conditions of at least about 150°C.
- the reaction when the above-described reaction solvent is used for preparing the lithium iron phosphate nanopowder, the reaction may be performed at a temperature less than or equal to the boiling point of the reaction solvent, and the vaporization degree of the reaction solvent may decrease.
- the pressure increase due to vaporization of solvents during the performing of the reaction may be significantly suppressed when compared to a common hydrothermal synthesis method. Therefore, safety throughout the process may be improved.
- the reactor may be a generally used reactor and may be an open type reactor or a closed-type reactor connected to a reflux, in which the pressure is not high, but is not limited thereto.
- the pressure conditions in Step (b) do not specifically require a pressure-resistant vessel that withstands a particularly high temperature and a high pressure.
- the supercritical hydrothermal synthesis method at least about 220 bar
- the glycothermal synthesis method from about 10 bar to about 100 bar
- the method of the present invention does not require a high-pressure-resistant reactor, thereby improving process safety and economic feasibility.
- Step (b) is performed at the temperature range of at least 150°C which is the minimum temperature for synthesizing the lithium iron phosphate nanopowder, and at a temperature range less than or equal to the boiling point of the reaction solvent used.
- reaction solvent used in the present invention is triethanolamine
- the above Step (b) is performed at about 150°C to about 335°C.
- the reaction is performed at a temperature between the minimum temperature for synthesizing the lithium iron phosphate nanopowder and a temperature less than or equal to the boiling point of the reaction solvent, and the vaporization of the reaction solvent is slowed down.
- the pressure increase of the reactor due to the vaporization of the solvent may be suppressed when compared to a common hydrothermal synthesis method, etc.
- the pressure in the reactor during the performing of the above Step (b) is in the range of 1 bar to 10 bar.
- the pressure is relatively lower when compared to that of the common hydrothermal synthesis method (at least about 100 bar), of the supercritical hydrothermal synthesis method (at least about 220 bar), or of the glycothermal synthesis method (from about 10 bar to about 100 bar), which provides even better effect when considering process safety and economic feasibility.
- the processing time of the above Step (b) may be changed according to the reaction temperature.
- the above Step (b) may be conducted at a temperature range of 150 to 335°C for 1 to 72 hours, and more particularly, may be conducted at a temperature range of 180°C to 335°C for 1 to 48 hours.
- Step (b) lithium iron phosphate nanopowder particle may be synthesized, and a washing step and a drying step for recovering the synthesized lithium iron phosphate nanopowder particle in Step (b) may be conducted sequentially.
- the washing method in the washing step is not specifically limited, and may be conducted sequentially by using acetone and methanol.
- the drying method in the drying step is not specifically limited, and may be conducted at a temperature range of 20°C to 160°C for 2 to 40 hours.
- the lithium iron phosphate nanopowder synthesized through the processes may be heat treated to form a coating layer on a portion or the whole of the surface of individual particle of the powder (Step (c)).
- the above Step (c) may be performed through heat treating.
- the heat treating is not specifically limited and is conducted by heating to a temperature range of 400°C to 900°C. Through the heat treating, a carbon coating layer or a coating layer composed of a glassy lithium compound may be formed on a portion or the whole of the surface of the particle.
- the precursor of the coating layer may be the reaction solvent remaining on the surface of the particle after use.
- the triethanolamine solvent used may remain on the surface of the particle after conducting the drying step and may be carbonized during the heat treatment at a temperature range of 400°C to 900°C, thereby forming the carbon coating layer on the surface of the particle.
- a separate organic compound may be used as the precursor of the carbon coating layer, and the addition step of the separate organic compound for forming the carbon coating layer on the surface of the lithium iron phosphate nanopowder particle is not specifically limited.
- the organic compound may be mixed with the solvent together with the lithium precursor, the iron precursor and the phosphorus precursor and react to form the carbon coating layer on the surface of the particle during the forming of the lithium iron phosphate particle.
- the lithium precursor, the iron precursor and the phosphorus precursor are mixed with the solvent and react to form the lithium iron phosphate particle, and then, the organic compound is added, mixed and heat treated to form the carbon coating layer on the surface of the particle.
- the lithium precursor, the iron precursor and the phosphorus precursor are mixed with the solvent and react to form the lithium iron phosphate particle, and washing and drying processes are performed. Thereafter, the organic compound is added, mixed and heat treated to form the carbon coating layer on the surface of the particle.
- the organic compound is not specifically limited, and may be at least one selected from the group consisting of glucose, sucrose, galactose, fructose, lactose, starch, mannose, ribose, aldohexose, ketohexose, and a combination thereof.
- the coating layer is not specifically limited, and may be, for example, a lithium phosphate-based amorphous coating layer.
- the precursor material may be a lithium precursor and a phosphorus precursor, and may be an additional lithium compound and phosphorus compound.
- the thickness of the carbon coating layer or the glassy lithium compound coating layer formed on the surface of the particle in this step is not specifically limited, and may be, for example, less than or equal to 10 nm.
- the electric conductivity of the lithium iron phosphate powder may be improved by forming the carbon coating layer or the coating layer including the glassy lithium compound on a portion of or the whole surface of the minute lithium iron phosphate powder particle thus prepared.
- the lithium iron phosphate nanopowder particle prepared through the series of the above-described steps may have an olivine structure.
- the particle size and the particle size distribution of the particle may be controlled by changing the lithium precursor, the iron precursor, or the phosphorus precursor, or regulating processing variables such as a reaction temperature and a reaction time, etc.
- the size of the lithium iron phosphate particle may decrease when using lithium acetate as the lithium precursor.
- the size of the lithium iron phosphate may increase when the reaction temperature is elevated or the reaction time is prolonged.
- the particle size (Hereinafter will be referred to as particle diameter) of the lithium iron phosphate nanopowder prepared through the above-described processes is not specifically limited, and may be, for example, from 30 nm to 300 nm.
- the particle size distribution is not specifically limited and may be, for example, less than or equal to 50% of the average value of the particle diameter.
- a cathode active material including the lithium iron phosphate nanopowder having the olivine crystal structure may be provided.
- the cathode active material may further include a conductive agent, a binder and a filler other than the lithium iron phosphate powder selectively.
- the conductive agent may include any material having conductivity and not inducing a chemical change in a battery without specific limitation, and may include graphite such as natural graphite and synthetic graphite; carbon blacks such as carbon black, acetylene black, ketchen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as a carbon fiber and a metal fiber; metal powders such as a carbon fluoride powder, an aluminum powder and a nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as a polyphenylene derivative.
- graphite such as natural graphite and synthetic graphite
- carbon blacks such as carbon black, acetylene black, ketchen black, channel black, furnace black, lamp black, and thermal black
- conductive fibers such as a carbon fiber and a metal fiber
- metal powders such as a carbon fluoride powder, an aluminum powder and a nickel powder
- conductive whiskers such as zinc oxide
- the conductive agent may be included by 1 wt% to 30 wt% based on the total amount of a mixture including the cathode active material.
- the binder may be any component that assists the bonding of the active material and the conductive agent and the bonding with a current collector without specific limitation, and may include, for example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, a styrene butadiene rubber, a fluorine rubber, various copolymers, etc.
- CMC carboxymethyl cellulose
- EPDM ethylene-propylene-diene monomer
- EPDM ethylene-propylene-diene monomer
- EPDM ethylene-propylene-diene monomer
- EPDM ethylene-propylene-diene monomer
- sulfonated EPDM a styrene butad
- the binder may be included by 1 wt% to 30 wt% based on the total amount of a mixture including the cathode active material.
- the filler is a component suppressing the expansion of an electrode and may be selectively used.
- the filler may be any fibrous material that may not induce a chemical change in the battery, without specific limitation, and may include, for example, an olefin-based polymer such as polyethylene and polypropylene; and a fibrous material such as a glass fiber and a carbon fiber.
- a cathode for a lithium secondary battery obtained by coating the cathode active material on a current collector is provided.
- the cathode for the lithium secondary battery may be fabricated by, for example, dissolving the cathode active material in a solvent to prepare a slurry, coating the slurry on the current collector, drying and pressing.
- the current collector of the cathode may be any material having conductivity and not inducing chemical change of a battery, without specific limitation, and may include, for example, stainless steel; aluminum; nickel; titanium; calcined carbon; or a surface treated material of the aluminum or the stainless steel with carbon, nickel, titanium, silver, etc.
- the current collector may have a thickness of 3 ⁇ m to 500 ⁇ m, and minute embossing may be formed on the surface of the current collector to increase the adhesiveness of the cathode active material.
- minute embossing may be formed on the surface of the current collector to increase the adhesiveness of the cathode active material.
- Various shapes such as a film, a sheet, a foil, a net, a porous material, a foamed material, a non-woven fabric, etc. may be used as the current collector.
- a lithium secondary battery including a cathode including the cathode active material, an anode, a separator and a non-aqueous electrolyte containing a lithium salt may be provided.
- the anode may be fabricated by, for example, coating an anode mixture including an anode active material on an anode current collector, and drying.
- anode mixture including an anode active material on an anode current collector, and drying.
- the above-described components such as the conductive agent, the binder and the filler may be included as occasion demands.
- the anode current collector may be any material having high conductivity and not inducing the chemical change of a battery, without specific limitation, and may include, for example, copper; stainless steel; aluminum; nickel; calcined carbon; a surface treated material of copper or stainless steel with carbon, nickel, titanium, silver, etc.; and an alloy of aluminum-cadmium.
- the current collector may have the thickness of 3 ⁇ m to 500 ⁇ m, and minute embossing may be formed on the surface of the current collector to increase the adhesiveness of the anode active material as in the cathode current collector.
- minute embossing may be formed on the surface of the current collector to increase the adhesiveness of the anode active material as in the cathode current collector.
- Various shapes such as a film, a sheet, a foil, a net, a porous material, a foamed material, a non-woven fabric, etc. may be used as the current collector.
- the separator is disposed between the cathode and the anode, and an insulating thin film having high ion transmittance and high mechanical strength may be used.
- the pore diameter of the separator may be generally from 0.01 ⁇ m to 10 ⁇ m, and the thickness thereof may be generally from 5 ⁇ m to 300 ⁇ m.
- the separator may include a chemical resistant and hydrophobic olefin-based polymer such as polypropylene; a sheet or a non-woven fabric formed by using a glass fiber or polyethylene, etc.
- a chemical resistant and hydrophobic olefin-based polymer such as polypropylene
- a sheet or a non-woven fabric formed by using a glass fiber or polyethylene etc.
- the solid electrolyte may also play the role of the separator.
- the non-aqueous electrolyte containing the lithium salt includes the electrolyte and the lithium salt, and the electrolyte may include a non-aqueous organic solvent or an organic solid electrolyte.
- the non-aqueous organic solvent may include, for example, aprotic organic solvents such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, ethyl propionate, etc.
- the organic solid electrolyte may include, for example, polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, a phosphoric acid ester polymer, poly agitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and a polymer containing an ionic dissociable group.
- the lithium salt may include a material favorably soluble in the non-aqueous electrolyte such as LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 C 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, a low molecular weight aliphatic lithium carbonate, lithium 4-phenylborate, imide, etc.
- a material favorably soluble in the non-aqueous electrolyte such as LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 C 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li
- the electrolyte may further include (for improving charge and discharge properties, and flame retardance, etc.), for example, pyridine, triethyl phosphite, triethanolamine, a cyclic ether, ethylenediamine, n-glyme, hexaphosphoric acid amide, nitrobenzene derivatives, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, an ethylene glycol dialkyl ether, an ammonium salt, pyrrole, 2-methoxyethanol, trichloro aluminum, etc.
- a halogen-containing solvent such as carbon tetrachloride, trifluoroethylene, etc. may be further included to impart incombustibility, and a carbon dioxide gas may be further included to improve preservation properties at a high temperature.
- the method for preparing the lithium iron phosphate nanopowder of the present invention may be performed at relatively lower pressure conditions when compared to a common hydrothermal synthesis method, a supercritical hydrothermal synthesis method or a glycothermal synthesis method by using a novel triethanolamine reaction solvent as a non-aqueous solution.
- a high temperature/high pressure reactor is not necessary, and process safety and economic feasibility may be secured, a uniform particle size may be attained, and a lithium iron phosphate nanopowder having controlled particle size distribution may be easily prepared.
- a lithium secondary battery including the lithium iron phosphate nanopowder thus prepared as a cathode active material may have good capacity and stability.
- LiOH lithium hydroxide
- FeC 6 H 5 O 7 ferric citrate
- H 3 PO 4 phosphoric acid
- the sufficiently stirred mixture solution was put into a 500 ml reactor and a reaction was respectively performed at 230°C for 24 hours.
- reaction product After finishing the washing and drying, the reaction product thus obtained was analyzed with an X-ray diffraction spectroscopy and a scanning electron microscope.
- the reaction product was confirmed to be a lithium iron phosphate nanopowder having a pure olivine crystal structure and including a mixture of particle having particle sizes of 30 nm and 100 nm (See FIGS. 1 and 2 ).
- the particle size distribution of the lithium iron phosphate nanopowder was measured and is illustrated as a graph in FIG. 3 . As shown in the graph, the particle size distribution is uniform.
- the lithium iron phosphate nanopowder prepared in Example 1 was heat treated in a furnace at 600°C (Example 2a) and at 700°C (Example 2b), respectively to obtain a lithium iron phosphate nanopowder including a carbon coating layer formed thereon.
- the reaction product thus obtained was analyzed with an X-ray diffraction spectroscopy and a scanning electron microscope.
- the reaction product was confirmed to be a lithium iron phosphate nanopowder having a particle size of 100 nm of pure olivine crystal structure when the heat treatment was performed at 600°C (Example 2a), and a lithium iron phosphate nanopowder having a particle size of 150 nm of pure olivine crystal structure when the heat treatment was performed at 700°C (Example 2b), respectively (See FIGS. 4 and 5 ).
- the lithium iron phosphate nanopowder prepared by the method of the present invention has small and uniform particle size and good particle size distribution properties.
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Claims (9)
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers, welches die Schritte umfasst:(a) Herstellen einer nicht-wässrigen Lösungsmischung durch Zufügen einer Lithiumvorstufe, einer Eisenvorstufe und einer Phosphorvorstufe zu einem nicht-wässrigen Triethanolamin-Lösungsmittel; und(b) Einführen der nicht-wässrigen Mischungslösung in einen Reaktor und Erwärmen, um das Lithiumeisenphosphatnanopulver unter Druckbedingungen von 1 bis 10 bar herzustellen,wobei Schritt (b) in einem Temperaturbereich von 150 bis 335°C durchgeführt wird.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, weiter umfassend den Schritt (c) eines Wärmebehandelns des Lithiumeisenphosphatnanopulvers in einem Temperaturbereich von 400 bis 900°C, um eine Beschichtungsschicht auf einem Bereich oder einer Gesamtheit einer Oberfläche eines einzelnen Teilchens des Nanopulvers zu bilden.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, wobei das in Schritt (b) hergestellte Lithiumeisenphosphatnanopulver aufeinanderfolgend gewaschen und getrocknet wird.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, wobei Schritt (b) bei einer Temperatur von weniger als oder gleich einem Siedepunkt des Triethanolamin-Lösungsmittels durchgeführt wird.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, wobei Schritt (b) für 1 bis 72 Stunden durchgeführt wird.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, wobei die Lithiumvorstufe wenigstens eine ist, ausgewählt aus der Gruppe bestehend aus Lithiumacetatdihydrat (CH3COOLi·2H2O), Lithiumhydroxidmonohydrat (LiOH·H2O), Lithiumhydroxid (LiOH), Lithiumcarbonat (Li2CO3), Lithiumphosphat (Li3PO4), Lithiumphosphatdodecahydrat (Li3PO4·12H2O) und Lithiumoxalat (Li2C2O4) oder einer Mischung aus zwei oder mehreren derselben.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, wobei die Eisenvorstufe wenigstens eine ist, ausgewählt aus der Gruppe bestehend aus Eisencitrat (FeC6H5O7), Eisencitrathydrat (FeC6H5O7nH2O), Eisen(II)sulfat-Heptahydrat (FeSO4·7H2O), Eisen(II)oxalat-Dihydrat (FeC2O4·2H2O), Eisenacetylacetonat (Fe(C5H7O2)3), Eisenphosphatdihydrat (FePO4·2H2O) und Eisen(III)hydroxid (FeO(OH)) oder einer Mischung aus zwei oder mehreren derselben.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 1, wobei die Phosphorvorstufe wenigstens eine ist, ausgewählt aus der Gruppe bestehend aus Triammoniumphosphattrihydrat ((NH4)3PO4·3H2O), Ammoniumphosphat ((NH4)2HPO4), Ammoniumdihydrogenphosphat (NH4H2PO4) und Phosphorsäure (H3PO4) oder einer Mischung aus zwei oder mehreren derselben.
- Verfahren zum Herstellen eines Lithiumeisenphosphatnanopulvers nach Anspruch 3, wobei das Trocknen bei 20 bis 160°C für 2 bis 40 Stunden durchgeführt wird.
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